Process for the manufacture of new xanthene dyes



Patented Nov. 1, 1932 um'rno STATES PATENT errce ALBERT COULTHARD AN DERNEST HARRY RODD, OF BLAGKLEY, MANCHESTER, ENGLAND, ASSIGNOBS T0IMPERIAL CHEMICAL INDUSTRIES LIMITED, 01 LONDON,

ENGLAND rnocnss ronrnn MANUFACTURE or NEWXANTHENE DYES No Drawing.Original application filed June 29, 1929, Serial No. 374,942. Dividedand this application filed. June 29, 1929, Serial No. 374,943, and. inGreatBritain July 7, 1928.

In British Patent No. 314,825 there is described the manufacture of newdyes by condensing 3: 7 tetra alkyldiaminoxanthones with aromatichalogen .compounds by means wherein R represents a phenyl or naphthylradical, R represents .a phenyl radical or an alkyl group and Rrepresents hydrogen or an alkyl group, and which contain a reactivenuclear hydrogen atom, xanthene dyes are obtained containing 3substituted 7 amino groups. These dyes which in the form of theirhydrochloride salts may be represented by the probable formula whereinIt represents an alkyl group, one R represents a phenyl or naphthylradical while the other R represents a phenyl radical or an alkyl groupand R represents hydrogen or an alkyl group, have advantageous dyeingproperties. In our copending application Ser. No 374,942 filed June 29,1929, of which the present application is a division, we have set forthand claimed these new Xanthene dyes and the process of making the same.v

The present application is directed to a process of sulphonating theseXanthene dyes described in ourabove-identified copending application andt0 the sulphonated dyes thus ro'duced.

WVe have now discovered that such basic dyes can be sulphonated to giveacid dyes having valuable properties. The most suitable basic dyes fortreatment according to our invention are those formed by thecondensation of amines which are known readily to yield sulphonatedproducts'when combined in other series, for instance, amines of thediphenylamine series. In particular the basic dyes obtained bycondensing 3:7- tetramethyldiaminoxanthene with p-tolylm-phenetidine orpara-tolyl m anisidine give when sulphonated acid dyestuifs dyeing wooland silk fine red shades. However we do not restrict" ourselves to theuse of any particular basic dyestuff of our new series and any one whichwillyield a soluble sulphonic acid derivative falls within the scope ofour invention. These dyestuffs dye wool and silk in red shades whichmaintain their shade well in artificial light compared, for instance,with'the dyeings obtained from acid rhodamines and when exposed to ultraviolet light become appreciably bluer'. One example illustrating amethod of carrying out our invention is the following: The parts are byweight:

EwampZe.-The basic dye which may be prepared by condensing together 3:7-tetramethyldiaminoxanthone and ptolyl-m'phenetidine by means ofphosphoryl chloride is well dried and finely powdered. This basic dyewhich in the form of the hydrochloride may be represented by theprobable structural formula N 0 -'Cl HaC 1 of the may be prepared as setforth in Example 2 of our copending application Ser. No. 374,942.

Of this dye 5 parts are stirred into 24 parts of 26 per cent oleum thetemperature being maintained below 5 C. The mixture is stirred for about6 hours or until sulphonation is complete which is the case when a testportion of the sulphonation' mixture when diluted with water and madealkaline by means of ammonia does not give rise to a precipitate. Thewhole is then poured onto 150 parts ice and parts salt, and neutralizedby the addition of about l i parts of caustic soda lye (40 per cent).The dye is precipitated usually as a flocoulent solid. It is filteredoil", pressed and dried at 100 C. It may be obtained as a greenishpowder, readily soluble in water. Its solution is somewhat redder thanthat of the unsulphonated basic dye. It dyes wool and silk a bright redshade which retains its shade well by artificial light. On exposure toultra violet light the dyeings become appreciably bluer. v

What we claim and desire to secure by Letters Patent is 1. In themanufacture of new sulphonated acid dyes of the xanthene type, theprocess which comprises sulphonating basic dyes of the xanthene typehaving in the form of the unsulphonated hydrochloride the probableformula wherein R represents an alkyl group, one R represents a phenylor naphthyl radical while the other R represents a phenyl radical or analkyl group and R represents hydrogen or an alkyl group; saidunsulphonated basic dyes being obtainable by condensing a 3 7tetra-alkyldiamino xanthone with an aromatic amine having the probableformula wherein R represents a phenyl radical, R represents a phenyl ornaphthyl radical or an alkyl group and R represents hydrogen or an alkylgroup, and which contain a reactive nuclear hydrogen atom, the saidcondensation being effected in the presence of a halogenated condensingagent capable of replacing the ketonic oxygen of the xanthone byhalogen.

2. In the manufacture of new unsulphonated acid dyes of the xanthenetype, the process which comprises sulphonating basis dyes xanthene typehaving in the form of the unsulphonated hydrochloride the probableformula wherein R represents an alkyl group, R represents a phenyl ornaphthyl radical and R represents a phenyl radical or an alkyl group;said unsulphonated basic dyes being obtainable by condensing3z'7-tetra-alkyldiaminoxanthones with aromatic amines having theprobable formula wherein R represents a phenyl or naphthyl radical and Rrepresents a phenyl radical or an alkyl group and which contain areactive nuclear hydrogen atom, the said condensation being effected inthe presence of a halogenated condensing agent capable of replacing theketonic oxygen of the xanthone by halogen.

3. In the manufacture of new sulphonated acid dyes of the Xanthene type,the process which comprises sulphonating basic dyes of the xanthene typehaving in the form of the unsulphonated hydrochloride the probableformula 'f ts wherein R represents a phenyl or naphthyl radical, Rrepresents a phenyl radical or an alkyl group and R represents hydrogenor an alkyl group, and which contain a reactive nuclear hydrogen atom,the said condensation being effected in the presence of a halogenatedcondensing agent capable of replacing the ketonic oxygen of the xanthoneby halogen.

4. In the manufacture of new sulphonated acid dyes of the xanthene type,the process which comprises sulphonating basic dyes of the Xanthene typehaving in the form of the unsulphonated hydrochloride the. probableformula a 1 r-N-Ra wherein R represents an alkyl group, R and Rrepresent phenyl radicals; said unsulphonated basic dyes beingobtainable by condensing 3 :7-tetra-alkyldiaminoxanthones with aromaticamines having the probable formula R1N-R2 1'1 wherein R and R representphenyl radicals and which contain a reactive nuclear hydrogen atom, thesaid condensation being effected in the presence of a halogenatedcondensing agent capable of replacing the ketonic oxygen of the Xanthoneby halogen.

5. The process of claim 1 in which the sulphonation is effected by meansof oleum.

6. The process of claim 2 in which the sulphonation is effected by meansof oleum.

7 The process of claim 4 in which the sulphonation is efiected by meansof oleum.

8. In the manufacture of new sulphonated acid dyes of the Kanthene type,the process which comprises sulphonating basic dyes of the Xanthene typehaving in the form of the unsulphonated hydrochloride the probableformula N-C1 R t wherein R represents an alkyl group, one R (5represents a phenyl or naphthyl radical while wherein R represents aphenyl or naphthyl radical, R represents a phenyl radical or an alkydgroup and R represents hydrogen or an alkyl group, and which contain areactive nuclear hydrogen atom the said condensation being effected inthe presence of phosphoryl chloride.

9. In the manufacture of new sulphonated acid dyes 'of the Xanthenetype, the process which comprises sulphonating a basic dye of theXanthene type having in, theform of the unsulphonated hydrochloride theprobable formula said unsulphonated basic dye being obtainable bycondensing 3:7-tetra-methyldiaminoxanthone withparatolyl-meta-phenetidine, said condensation being eflected in thepresence of phosphoryl chloride.

11. As new products, new sulphonated acid dyes of the Xanthene typewhich may be obtained by sulphonating basic dyes of the Xanthene typewhich have in the form of the unsulphonated hydrochloride the probableformula wherein R represents an alkyl group, one R represents a phenylor naphthyl radical while the other R represents a phenyl radical or anallryl group and R represents hydrogen or an alkyl group, the said newsulphonated acid dyes dyeing wool in red shades which become appreciablybluer when exposed to ultra violet rays. i

12. As new products, new sulphonated acid dyes of the Xanthene typewhich may be ob tained by sulphonating basic dyes of the Xanthene typewhich have in the form of the unsulphonated hydrochloride the probableformula O \N =l I' 01 R 1'1 wherein R represents an alkyl group, Rrepresents a phenyl or naphthyl radical and R represents a phenylradical or an alkyl group, the said new sulphonated acid dyes dyeingwool in red shades which become appreciably bluer when exposed to ultraviolet rays.

13. As new products, new sulphonated acid dyes of the Xanthene typewhich may be obtained by sulphonating basic dyes of the Xanthenc typewhich have in the form of the unsulphonated hydrochloride the probableformula CH3 7 H3 C O N :fr- 01 H3 0 (IDES wherein R represents a phenylor naphthyl radical and R represents a phenyl radical or an alkyl group,the said new sulphonated acid dyes dyeing wool in red shades whichbecome appreciably bluer when exposed to ultra violet rays.

15. As new products, new sulphonated acid dyes of the Xanthene typewhich may be obtained by sulphonating basic dyes of the Xanthene typewhich have in the form of the unsulphonated hydrochloride the probablewherein R represents an alkyl group, R and R represent phenyl radicals,the said new sulphonated acid dyes dyeing wool in red shadeswhich'become appreciably bluer when exposed to ultra violet rays.

16. As new products, new sulphonated acid dyes of the Xanthene typewhich may be obtained by sulphonating basic dyes of the xanthene typewhich have in the form of the unsulphonated hydrochloride the probableformula wherein R and R represent phenyl radicals,

the said new sulphonated acid dyes dyeing wool in red shades whichbecome appreciably bluer when exposed to ultra violet rays.

17. As new products, new sulphonated acid dyes of the Xanthene typewhich may be obtained by sulphonating basic dyes of the Xanthene typewhich have in the form of the unsulphonated hydrochloride the probableformula wherein R represents an alkyl group, R represents an alkoxygroup, the said new sulphonated acid dyes dyeing wool in bright redshades which become appreciably bluer when exposed to ultra violet rays.

18. As new products, new sulphonated acid dyes of the xanthene typewhich may be obtained by sulphonating basic dyes of the Xanthene typewhich have in the form of the unsulphonated hydrochloride the probableformula H3 0 O I \N ITT 01 mo CH3 H-fFO' on;

wherein R represents an alkoxy group, the

said new sulphonated acid dyes dyeing wool in bright red shades whichbecome appreciably bluer when exposed to ultra violet rays.

19. As new products, new sulphonated acid dyes of the Xanthene typewhich may be obtained by sulphonating basic dyes of the xanthene typehaving in the form of the unsulphonated hydrochloride the probableformula wherein R represents an alkyl group, said new sulphonated aciddyes dyeing wool in bright red shades which become appreciably bluerwhen exposed to ultra Violet rays.

20. As new products, new sulphonated acid dyes of the Xanthene type,which may be obtained by sulphonating basic dyes of the Xanthene typewhich have in the form of the unsulphonated hydrochloride the probableformula on 0 I 3 /N N- 01 H O 23H:

said new sulphonated acid dyes dyeing wool in bright red shades whichbecome appreciably bluer when exposed to ultra violet ray.

21. In the manufacture of new sulphonated acid dyes of the Xanthenetype, the process which comprises sulphonating a basic dye of theXanthene type having in the form of the unsulphonated hydrochloride theprobable formula wherein R represents an alkyl group and R represents analkoxy group; said unsulphonated basic dye being obtainable bycondensing a 3:7-tetra-alkyldiaminoxanthone with an aromatic aminehaving the probable formula the said condensation being effected in thepresence of phosphoryl chloride.

22. In the manufacture of new sulphonated acid dyes of the Xanthenetype, the process which comprises sulphonating a basic dye of theXanthene type having in the form of the unsulphonated hydrochloride theprobable formula y R 0 R R V V R o H-N-OOHa wherein R represents analkyl group, said new sulphonated acid dyes dyeing wool in bright redshades which become appreciably bluer when exposed to ultra violet rays.

2 As new products, new sulphonated acid dyes of the Xanthene type whichmay be obtained by sulphonating basic dyes of the Xanthene type whichhave in the form of the unsulphonated hydrochloride the probable formulaH3C\ O I /N 01 i HaO (5H;

OOH:

said new unsulphonated acid dyes dyeing wool in brightred shades whichbecome appreciably bluer when exposed to ultra violet rays.

25. In the manufacture of new sulphonated acid dyes of the Xanthenetype, the process which comprises reacting with 26 per cent oleuni orits equivalent, the condensation product of a 3:Y-tetra-alkyldiaminoxanthone with an amine selected from a classconsisting of secondary and tertiary amines having a reactive nuclearhydrogen atom, the said condensation being effected in the presence of ahalogenated condensing agent capable of replacing the ketonic oxygen ofthe Xanthone by halogen; whereby the said condensation product becomessulphonated.

In testimony whereof we afiix our signatures.

ALBERT COULTI-IARD. ERNEST HARRY RODD.

Certificate of Correction Patent No. 1,8 5,592. a November 1,1932.

ALBERT OOULTHARD ET AL.

It is hereby certified that error appears in the printed specificationof the abovenuinbered patent requiring correction as follows: In thetitle and throughout the specification for Xanthene read wanthen; page 2line 53, claim 1, after phenyl insert the Words or naphthyl; and line 51, strike out the Words or naphthyl line 62, claim 2, for unsulphonatedread sulphonated; line 64, for basis read basic; and lines 68 to 74,strike out the formula and insert instead:

R1N-R2 1i page 5, line 55, claim 21, for the last two letters of theformula CH read CH and line 127, claim 24:, for unsulphonated readsulphonatecl and that the said Letters Patent should be read with thesecorrections therein that the same may conform to the record of thecasein the Patent Ofiice.

Signed and sealed this 6th day of December, A. D. 1932.

SEAL M. J. MOORE;

Acting Commissioner of Patents.

